Diffusion-resistant purple color couplers for the preparation of photographic color pictures

ABSTRACT

A color photographic material having a layer sensitized for green and containing developers for forming the purple image and containing an anilino-pyrazolone coupler.

United States Patent [191 Meier et al.

[73] Assignee: Afga-Gevaert Aktiengesellschaft,

Leverkusen, Germany 22 Filed: Aug. 27, 1971 21 Appl.No.: 175,703

[30] Foreign Application Priority Data Aug. 29, 1970 Germany 2042922 52 us. Cl. 96/100 51 Int. Cl G03c 1/40 58 Field of Search 96/100, 56.5

[4 1 Apr. 30, 1974 [56] References Cited 4 UNITED STATES PATENTS 3,677,764 7/1972 Glockner et al. 96/56.5 2,983,608 5/l96l Beavers.....-. 96/100 3,127,269 3/1964 Greenhalgh et al. 96/100 FOREIGN PATENTS OR APPLICATIONS 1,035,959 7/1966 Great Britain 96/100 Primary Examinef-J. Travis Brown Assistant Examiner-Richard L. Schilling Attorney, Agent, or Firm-Arthur G. Connolly [57] ABSTRACT A color photographic material having a layer sensitized for green and containing developers for forming the purple image and containing an anilino-pyrazolone coupler.

2 Claims, No Drawings 1 DIFFUSION-RESISTANT PURPLE COLOR COUPLERS FOR THE PREPARATION OF PHOTOGRAPI-IIC COLOR PICTURES BACKGROUND OF THE INVENTION This invention relates to novel diffusion-resistant color components or couplers which react with oxidation products of developers of the p-phenylene diamine type to purple dyestuffs. They are employed in the green-sensitive layer of photographic materials, especially multi-layer color materials.

It is known that for purple components it is possible to use derivatives of 1-phenyl-3-anilino-pyrazolone- ,(5 such as are disclosed in the U.S. Pat. Nos. 2,983,6-

08 and 3,127,269, in the commonly owned U.S. application Ser. No. 849,498 filed Dec. 8, 1969, now U.S. Pat. No. 3,677,764, by Hans Glockner, Ernst Meier and Walter Puschel and in the Netherlands Pat. No. 6,413,277.

These patents disclose water-soluble and waterinsoluble components. The water-insoluble couplers contain a diffusion-preventing radical, mostly bound by an acylamino grouping. According to known methods,

such couplers are dispersed with the aid of wetting agents and if necessary oil formers into gelatin and in this form are added to the silver halide emulsion. The Netherlands Patent No. 6,413,277 discloses anilinopyrazolone couplers wherein the diffusion-preventing radical is directly bound to the phenyl radical of the aniline group. In addition the couplers contain a sulfo group in the aniline radical. Such couplers may be added to the emulsion in the form of the aqueous solution of an alkali salt.

SUMMARY OF THE INVENTION It has now been determined, according to the invention, that anilino-pyrazolones of the generalformula:

are very well suited as color components for the preparation of purple color formers. In the above formula R is H or one or several substituents, customary to -p q -p aaplqnss s c as l xl-ial sqxyrl a I Absorptions, maximum: 535 mu kylothio-, phenoxy-, halogen-, carboxy-, sulfo acidalkylsulfono-, carbalkoxy-, carbamido-, sulfofluorido-, cyano-, nitrogroups;

R is alkyl, aryl, O-alkyl, O-aryl, NH-alkyl, NH-aryl,

where alkyl and aryl may be substituted if necessary, and R contains particularly a diffusionpreventing group in the form of one or several straight, branched or cyclic hydrocarbon radicals with collectively at least eight carbon atoms;

5 is H or h alogen-, alkyl-, alkgx yg, alkylthio group;

R is H or a radical, separable in the developing, such as Cl, 1-1 or a substituted phenylazo group, as the case may be;

n is l or 2.

The novel purple components are advantageously distinguished over the known anilino-pyrazolone components in many respects. They contain an acylamino grouping which advantageously affects the photographic properties and by means of which the diffusionpreventing radical may be introduced in particular abundance. The sulfo group enables the introduction of the components into the photographic emulsion without special dispersion steps and without the aid of special dispersing additives. In this manner. a high degree of dispersion is achieved with these couplers. In addition, the sulfo group affects exactly in the aniline radical in the advantageous manner the spectral properties of the purple coloring substances: Undesired secondary absorptions, in comparison to the unsulfonated components, are lessened, and the position of the absorption maximum may be affected depending at which point in the aniline radicalthe sulfo group is introduced. This last-named advantage shows up less in the absorption.

in solvents than in the use in the photographic layer.

DETAILED DESCRIPTION OF THE INVENTION As examples for the novel color components, the following are cited. The figures given signify the absorption maximum in m twith N,N-diethyl-3-methyl-pphenylene diamine in butanol.

- The novel purple compon nt s react W611 with the oxidation product of all customary developers of XI Absorptions, mziximum: 530 111;: S 0 H NH NH(I?-CH (BO N C=O g 1 T Cm ss 0 III Absorplious, maximum: 536 111;: S 01H CmHaa IV Absorptions, maximum: 534 m u IIOJS NH%CH2 1 N 5:0 NH N 0 I 0 Cl CI 01011::

V Absorptions, maximum: 537 m S -NH(HJCH2 N 5:0 NH $0 1 A) Cl $15K VI Absorptions,max1mum:543mu HOaS NHIC-CH2 A, S OzCnHna VII Abso tions, maximum: 536 mu HOaS-N11(||J-?Hz IlIH N\ /C=O I N I C O 1 S ozCloHu VIII. Absorptions, maximum: 534.5 mu

I IH

I N ([30 IIIH C1- C1 Cls ar IX Absorptions, maximum: 530.5 ma S 0 11 NH-fi(|JH2 1 :11

I N (I) O 0 2):

Cn n

X Absorptions, maximum: 538 my IS OaH ii I l H CH 0:0

3 N I CnHu C1 S OaH XI Absorptions, maximum: 536 mu. Absorptions, maximum: 424 m (prior to S 03H uncoupling). I III N (I) O C1 C1 Cie za XII. Absorptions, maximum: 532 m Component contains 1.5 equivalent sulfo (S OaH)1.5

groups and is a mixture of monoand disulto acid.

(IDONH NH(]] --C H: I I k =0 H2): 11

01 -01 Cit si The components of the invention may be. used both 60 and 1,134,329 and the commonly owned U.S. applicain the negative/positive process as well as in the reverse v tion Ser. No. 849,498 filed Dec. 8, 1969 by Hans Glockner, Ernst Meier and Walter Puschel.

These couplers are made by reacting an amino anilino pyrazolone with a chloroformic acid ester. Examples of suitable esters of the chloroformic acid are for instance the following: ethylester, 2'-hexylnonylester, hexadecylester, 4-bromobutylester; cyclohexylester, tetrahydrofurfurylester; phenylester, p-

nitrophenylester, p-dodecylphenylester, n-pentadecylphenylester, 2,4-dichloro-6-tetradecylphenylester, ooctadecyloxy -phenylester, p-chloro-o-tetradecylphenylester; p-butylphenoxyethylester, 2-butyl-4-nonylphenylester, m-pentadecylphenoxyethylester, pdodecyloxyphenoxypropylester, 4 chloro-3-methyl-6- tetradecylphenoxypropylester.

For example, 7.4 g of 1-(2',4,6'-trichlorophenyl)-3 (4"-aminoanilino)pyrazolone-(5) which has been described in US. Pat. No. 2,983,608, were dissolved while stirring in ml pyridine and then reacted at 20C with 8 g of 4-chloro-2-tetradecylphenylchloroformate. The temperature during this step rose to C. Stirring was continued for 40 minutes without application of heat. The mass was then poured into a mixture of ml of concentrated hydrochloric acid, ml methanol and 80 ml ethylacetate and was stirred for 5 minutes. After adding ml water, the ethylacetate layer was separated and shaken out with dilute hydrochloric acid and water. The solvent was removed by evaporation and the oily residue was taken up in petroleum ether, and the residue precipitated after cooling.

These couplers are then subjected in a known manner to a sulfonation process. Sulfonation agents, for example, are concentrated sulfuric acid or chlorosulfonic acid. In this connection, the sulfonation agent may be added to the unsulfonated coupler or also in reverse. Analytical investigation shows that the sulfonation preferably takes place in the aniline portion of the molecule. A sulfo group initially set in in the 4-position of the molecule (coupling point) is again separated in the working up.

With this method of subsequent sulfonation, one obtains no homogeneous products but instead mixtures of position-isomeric monoand disulfo acids. These mixtures may be separated into the individual constituents, by chromatography, for example. This separation process, however, is cumbersome and is mostly not required in the practice for employment of the components.

1f homogeneous components according to the present invention are to be prepared wherein the placing of the components of the sulfo groups is clear, one must start with defined intermediate sulfonation products with respect to the pyrazolone synthesis. Unfortunately, in this instance, most of the known methods for the preparation of anilinopyrazolones fail. However, the reaction of aniline sulfo acids with B,B,B-trialkoxypropionic acid esters well achieves its goal.

3-anilino-pyrazolone-(5) of the general fonnula may be prepared by reacting a B,B,B-trialkoxy propionic acid alkyl ester of the general formula RQO7CCHQCOORI 7 R o with an aniline of the formula LII 8 and condensation of the intermediate productobtained with a hydrazine of the formula Il -NH NH2 5 In these formulae R is alkyl, aralkyl, aryl, if necessary substituted by one or several alkyl-, alkoxy-, alkylthio-, phenoxy-, halogen-, carboxy-, sulfo acid-, alkylsulfonic, carbalkoxy-, carbamide-, su1fofluoride-, cyano-, nitro groups R is 1-1 or one or several substituents such as an alkylalkoxy-, alkylthio-, halogen-, caboxy-, sulfo aeid-, alkylsulfonic-, carbamido-, acylamino-, sulfofluorido-, cyano-, nitro group R is short-chain alkyl with one to four carbon atoms, alike or R different.

The B,B,B-trialkoxy propionic acid esters, used according to the invention, may also be designated chemically as semi-orthoesters of malonic acid. A compound of this sort of B,B,B-triethoxypropionates is described by McElvain, Schroeder, Am. Soc. 71, 1949, pp. 44-45. The correspondingtrimethoxy propionic acid ethyl ester is very stable in pure form and may be employed particularly well according to the invention.

The particular advantage of the new process is that with the aid of such ortho esters, even acid anilines, such as sulfanilines for example, may be called upon with good yield for the synthesis of 3- anilinopyrazolones-( 5 Quite generally, the following anilinesmay for example be reacted with the orthoesters: Aniline, 4-

chloraniline, 2,4-dichloraniline, m-tuluidine, pdodecylaniline, m-nitroaniline, sulfanilic acid, 2-amino-4-nitrobenzene sulfonic acid, 2-nitro-4- aminobenzene sulfonic acid, 2-nitro-4-chlor-5- aminobenzene sulfonic acid.

The reaction of the aniline with the orthoester takes place at temperatures between 20 and 100C, preferably in the presence of glacial acetic acid. The yields of the intermediate product obtained, B-alkoxy-B-anilino acryclic acid ester, are nearly quantitative. In most instances, a purification with hydrazine prior to the reaction is eliminated.

Suitable hydrazines for a pyrazone synthesis are, for example, phenyl hydrazine, m-chlorphenyl hydrazine, 2,4,6-trichlorophenyl hydrazine, p-nitrophenyl hydrazine, 2-nitro-4-trifluoromethylphenyl hyrdazine, 2- cetyloxyphenyl hydrazine, 4-hydrazino-phenylcetylfulfone, 4-chloro-5-hydrazino-phenylchloromethylsulfone, phenylhydrazine-m-sulfonic acid, ethyl-hydrazine, benzyl hydrazine, 2-chlorobenzyl hydrazine.

EXAMPLE 1 Purple Components of Formula lll First Step l-(2,4,6-trichlorphenyl)-3(3 -nitro-6' -sulfoanilino)-pyrazolone-(5) Na salt A mixture of 48 g (0.2 mol) 2-amino-4-nitro-benzene-sulfonic acid sodium (dry and finely pulverized), 8.2 g (0.1 mol) sodium acetate (dry), 100 ml glacial acetic acid and 66 g (0.34 mol.)B,[3,B-trimethoxy propionic acid ethyl ester were stirred at 80C bath temperau unti di SQUEQ-Jhfltth glaq a sq fi-f a w distilled off under reduced pressure. The viscous residue was dissolved in 850 ml methanol and heated on a water bath with 42.3 g 2,4,fi-trichlorphenyl-hydrazine.

tion, after acidifying with glacial acetic acid, there were.

precipitated 50 g nitropyrazolone 50 theoretical.

Second Step l-(2',4',6-trichlorphenyl)-.3-( 3 -amino-6' -sulfoanilino)-pryazolone-( 50 g Nitro compound from Step 1 were introduced into 100 g SnCl '2H O with 200 ml HCl concentrated at 85l00C during stirring. The stirring was continued at 95C for another minutes after the completion of the reaction. The white precipitate was drawn off upon cooling and washed with percent BC]. The moist crude product was mixed with methanol and again drawn off. The free amine was obtained by dissolving in water/alkali and precipitating with an excess of glacial acetic acid.

Yield: 36 g 80 percent of the theoretical. Third Step I Purple Component Formula lll To a solution of 22.5 g aminopyrazolone in 80 ml pyridine there were added while stirring 18 g of chloro-formic-acidcetylester and heated to 50C for one hour. The pyridine solution was poured over 300 ml 1 12 percent HCl, the precipitated deposit drawn off and washed with thinned HCl and water. The dried crude product was dissolved in methanol with the addi tion of pyridine. The filtered solution was acidified with percent of the hydrochloric acid to ,,l-l l. The precipitated coupler was drawn off and washed with methanol. Yield: 23.5 g.

Photographic Application of the Color Component First, a solution of the coupler was prepared in the customary manner in that it was suspended in methanol and mixed with thinned soda lye. This solution was added to a silver halide emulsion. Thereupon, it was poured ona carrier and dried. The photographic film obtained was illuminated under a stepped photometric absorption wedge and was subjected to a color negative developing process. The developing substance was N,- N-diethyl-3-methyl-p-phenylenediamine. Thereupon, the film was treated in a bleaching solution and in a fixing solution and dried. Obtained was a negative purple picture. Absorption maximum 540 mp.

If the film is subjected to a color reversal process after exposure, there is obtained a corresponding positive purple picture.

EXAMPLE 2 After the development of both color componentslll and IV in a photographic silver halide film, the following absorption maxima were measured with various color developing substances:

Developing substance Component Ill Component lV N,N-diethyl-p-phenylene 533 mp. 520 mp.

'amine N,N-diethyl-3-methyl- 540 mp. 527 my. p-phenylenediamine 4-amino-3-methyl-N- 539 my. 515 my.

'ethyl-N-methane sulfonamidoethyl anilin As shown by this table, the absorptions with respect to component IV as compared to the position-isomeric component 111 have a shift toward shorter waves.

EXAMPLE 3 Purple Component of Formula Xll 160 g Unsulfonated purple component according to Example 3 of the US. Appln. Ser. No. 849,498 referred to above were finely ground and introduced in 96 percent into 400 ml sulfuric acid at 20C during stirring. After stirring at room temperature for 4 hours, the solution was stirred into 4.5 1 water. The precipitated deposit was separated and dissolved in 4 1 hot water. By the addition of 400 ml HCl conc., the component is again precipitated. After repeated dissolving and reprecipitating, no further 80., ions could be detected. The separated precipitate was dried and finely ground. After anotherdrying under reduced pressure, 170 g of the component were obtained.

By analytical investigation it was determined that the sulfonation had taken place in the aniline radical of the molecule and that a mixture exists consisting of monoand disulfonic acids. The 1-! content was yielded in 14.7%; this corresponds to about 1.5 SO l-l equivalents.

The components may be dissolved in water in the customary manner with the aid of alkali. Added to a sil- EXAMPLE 4 Screened Component of Formula Xl,

12.3 g (0.1 mol) p-anisidin, ml HCl 5n and 60 ml H 0 were diazotized at 0C with 6.9 g (0.1 mol) NaNO and 20 ml I1 0. The diazonium solution was allowed during stirring to flow into a solution of 82.5 g components of Example 1 (Formula 11]) in 1400 ml pyridine. After 30 minutes at room temperature, it was stirred into a mixture of 2000 ml HCI cone. and 3 kg ice. The precipitate was drawn off and washed well with thinned HCl and H 0. The dry crude product was stirred for p t on. with. 5 991299 at a wat ba h Yield: 65 g The component, a yellow-colored azo dyestuff, has an absorption miximum of 424 mp. (screened compo nent).

For photographic application, the screened component was dissolved in water as lithium salt and incorporated in a green-sensitive negative emulsion. The emulsion was poured as a partial layer of a multi-film negative material. Dried and pictorially illuminated with green light; after customary processing in a color negative process using 4-amino-3-methyl-N-ethyl-N- methane sulfonamidoethyl aniline as the developing substance obtained was a negative purple picture. Ab-

sorption maximum: 539 mu. At the same time there re-' eliminating the blue absorption of the corresponding purple dye image. it is noteworthy the good coupling of the masking coupler as well as the good stability of the mask in the bleaching bath.

What is claimed is:

l. in a photographic silver halide emulsion layer optically sensitized to the green region of the spectrum and containing developers that form purple dyestuffs, the improvement according to which the emulsion contains a coupler component of the following formula:

l )n Ra In this formula 7 V R is H, Cl, SO l-i, phenylazo;

2. In a photographic silver halide emulsion as defined in claim I, a mixture of monoand disulfoacids of the' ?"P rompq nt- 

2. In a photographic silver halide emulsion as defined in claim 1, a mixture of mono- and disulfo- acids of the coupler component. 